CN113015582B - Polymer for metal surface treatment - Google Patents
Polymer for metal surface treatment Download PDFInfo
- Publication number
- CN113015582B CN113015582B CN201980074620.0A CN201980074620A CN113015582B CN 113015582 B CN113015582 B CN 113015582B CN 201980074620 A CN201980074620 A CN 201980074620A CN 113015582 B CN113015582 B CN 113015582B
- Authority
- CN
- China
- Prior art keywords
- polymer
- coating
- conversion
- metal surface
- varnish
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 69
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 239000002184 metal Substances 0.000 title claims abstract description 51
- 238000004381 surface treatment Methods 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 239000002966 varnish Substances 0.000 claims abstract description 23
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000853 adhesive Substances 0.000 claims abstract description 18
- 230000001070 adhesive effect Effects 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- FHEHIXJLCWUPCZ-UHFFFAOYSA-N 4-prop-2-enylbenzene-1,2-diol Chemical compound OC1=CC=C(CC=C)C=C1O FHEHIXJLCWUPCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004922 lacquer Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- PARWTEYYJSDGQM-UHFFFAOYSA-N 3-prop-2-enylbenzene-1,2-diol Chemical compound OC1=CC=CC(CC=C)=C1O PARWTEYYJSDGQM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000007739 conversion coating Methods 0.000 claims description 26
- 239000003973 paint Substances 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 13
- 239000010410 layer Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 229910000838 Al alloy Inorganic materials 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000012790 adhesive layer Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 7
- 229920002125 Sokalan® Polymers 0.000 description 5
- -1 fluoride ions Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000001542 size-exclusion chromatography Methods 0.000 description 4
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000000569 multi-angle light scattering Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KUQRLZZWFINMDP-BGNLRFAXSA-N 2-[(3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O KUQRLZZWFINMDP-BGNLRFAXSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/22—Oxygen
- C08F212/24—Phenols or alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/20—Metallic substrate based on light metals
- B05D2202/25—Metallic substrate based on light metals based on Al
Abstract
The invention relates to polymers obtained by free radical copolymerization of a mixture of: (1) acrylic acid; (2) methacrylic acid; and (3) at least one allylcatechol selected from the group consisting of 4-allylbenzene-1, 2-diol, 3-allylbenzene-1, 2-diol, and mixtures thereof. These polymers are particularly useful for treating metal surfaces intended to be coated with lacquers, varnishes or adhesives. The invention also relates to coating methods using this polymer P, compositions comprising this polymer P and useful in these methods, and the resulting coated materials.
Description
The present invention relates to the field of treatment of metal-based surfaces, and in particular metal surfaces intended to be coated with film-forming organic compositions such as lacquers, varnishes or adhesive compositions. The invention relates more particularly to the treatment of said metal surfaces with the aim of providing protection, in particular against corrosion, and/or enhancement of the adhesion of film-forming organics.
In order to provide such effects on metal surfaces, in particular on aluminum or steel, several methods have been proposed, including in particular the deposition of inorganic coatings, in particular so-called "conversion coatings", on metal surfaces.
The term "conversion coating" is well known in the art and refers to a layer formed on a metal surface, which is an advantageous alternative to natural oxides on said surface, in particular on aluminum, and which is obtained by a controlled chemical formation of a film on the metal surface by reaction with chemical elements of the metal surface, such that at least some of the cations dissolved from the metal material are deposited in the conversion coating.
Typically, the coating (such as a conversion coating) is obtained by reacting a metal surface with a solution containing metal cations and fluoride ions. In the past, chromium-containing coatings have been proposed (typically by contacting a surface with a coating comprising H 2 CrF 6 Obtained by solution reaction of (a) and more recently it has been proposed to base on less toxic coatings such as zirconium, titanium or other metals (for example by bringing the surface into contact with a coating comprising H) 2 TiF 6 、H 2 ZrF 6 、H 2 HfF 6 、H 2 AlF 6 、H 2 SiF 6 、H 2 GeF 6 、H 2 SNF 4 Or HBF 4 Obtained by solution reaction). The conversion coating may comprise other compounds such as, for example, silane precursors.
In order to enhance corrosion resistance and paint adhesion on coatings such as conversion coatings, it is known to add some additives, especially organic polymers. In this connection, the use of polyacrylic acid has been described, for example. Typical additives are those obtained from Dow (DOW) (and from the previous Rohm Haas company (Rohm)&Haas)) available ACUMER TM 1510 have been widely described for such applications. For more details on this, reference is made in particular to WO 97/13588, US 4,191,596 or US 4921552.
It is an object of the present invention to provide a new method for treating metal surfaces which gives good corrosion protection to the metal surfaces and gives good adhesion to film forming organic compositions applied to the metal surfaces, such as lacquers, varnishes or adhesive compositions.
For this purpose, the invention proposes the use of specific polymers, preferably together with the formation of the conversion coating (i.e. before, during or after), which advantageously lead to the formation of a treated metal surface, which has been shown to be of great interest: when coated with a film-forming composition such as a paint, varnish or adhesive composition, good adhesion is obtained between the surface and the coating composition. In addition, good protection of the surface, in particular corrosion resistance, is obtained.
More precisely, the invention uses at least one polymer P, which is
A polymer obtained by free radical copolymerization of a mixture of:
-Acrylic Acid (AA);
methacrylic acid (MAA); and
-at least one allylcatechol selected from the group consisting of 4-allylbenzene-1, 2-diol; 3-allylbenzene-1, 2-diol, and mixtures thereof.
The compounds 4-allylbenzene-1, 2-diol and 3-allylbenzene-1, 2-diol have the following formula, respectively:
the polymer P typically contains as a mixture of these two isomers of the allylcatechol typically has a molar ratio of 4-allylbenzene-1, 2-diol to 3-allylbenzene-1, 2-diol of between 30/70 and 70/30, for example between 50/50 and 70/30.
The polymer P preferably contains Acrylic Acid (AA) in an amount of 10 to 90% by mol; methacrylic acid (MAA) in an amount of 1 to 70% by mol, and allylcatechol in an amount of 1 to 20% by mol, each molar ratio being calculated based on the total amount of AA, MAA and allylcatechol.
The molecular weight of the polymer P is typically between 10 and 150kDa, for example between 15 and 100 kDa.
According to a specific embodiment, the polymer P contains allylcatechol in an amount of 1 to 5% mol. In this case, the polymer P generally contains MAA in an amount of up to 70% mol and has a molecular weight M of 80kDa or less w 。
According to another embodiment, the polymer P contains allylcatechol in an amount of 5 to 10% mol. In this case, the polymer P generally contains MAA in an amount of up to 40% mol and has a molecular weight M of 40kDa or less w 。
According to another embodiment, the polymer P contains allylcatechol in an amount of 10 to 15% mol. In this case, the polymer P generally contains MAA in an amount of up to 20% mol and has a molecular weight M of 30kDa or less w 。
According to another embodiment, the polymer P contains allylcatechol in an amount of 15 to 20% mol. In this case, the polymer P generally contains MAA in an amount of up to 10% mol and has a molecular weight M of 20kDa or less w 。
According to a first aspect, the polymers P as described above, which form the subject of the present invention, are not described in the art, with the knowledge of the inventors.
Within the scope of the present invention, the inventors have now observed that the use of polymer P gives protection and improved adhesion between the metal surface and the paint applied on the surface, these ratios being compared to the use of common additives such as ACUMER TM 1510 are better than those observed.
According to a particular aspect, a particular object of the present invention is the use of at least one polymer P as defined above for treating a metal surface intended to be coated with paint, varnish or adhesive. The metal surface to be treated is preferably a surface comprising a metal selected from the group consisting of aluminum, steel, zinc, magnesium and alloys thereof. Of particular interest to the present invention are metal surfaces of aluminum or aluminum alloys.
According to an embodiment of interest, the conversion coating is applied to the metal surface to be treated (in other words, the conversion composition is applied to the metal surface to form the conversion coating thereon) by reacting the surface with the conversion composition. In this case, typically:
the conversion composition comprises all or part of the polymer P as additive; and/or
-applying the conversion coating on the metal surface and then applying all or part of the polymer P on the conversion coating.
According to another possible embodiment (compatible with the previous one), all or part of the polymer P is present in a paint, varnish or coating applied on the surface, preferably after the conversion coating has been applied on the metal surface.
According to another aspect, another specific object of the invention is a process for coating a metal surface with paint, varnish or adhesive, preferably with paint, comprising a step of treating said surface with at least one composition comprising at least one polymer P as defined above. Within the stated ranges, the composition comprising polymer P may typically be:
-a conversion composition comprising a polymer P; and/or
-a solution or dispersion of the polymer P, preferably applied on the surface to be treated after the application of the conversion coating on the surface; and/or
A paint, varnish or adhesive which may comprise all or part of the polymer P.
Conversion compositions comprising the polymer P and lacquers, varnishes or adhesives comprising the polymer P also constitute a particular object of the invention.
Typically, the polymer P is present in the conversion composition and/or in a solution or dispersion applied over the conversion coating. In this case, a lacquer, varnish or adhesive is applied to the surface previously treated with the polymer. According to some specific embodiments, an additional layer may be applied between the treated surface and the lacquer, varnish or adhesive (this is the case, for example, when a metal foil is treated at a first site and then has to be coated, for example, lacquered, at a second site: in this case a lubricant may be applied to the treated foil in order to allow rolling of the foil and ease its transportation).
According to yet another aspect, a specific object of the invention is a material comprising a metal surface which is wholly or partly (i) treated with a polymer P as defined above and (ii) covered with a lacquer, varnish or adhesive.
These materials include materials having, inter alia, a metallic surface that is wholly or partially covered by:
at least one coating (typically a conversion coating and/or a paint, varnish or adhesive layer) comprising at least one polymer P;
and/or
A layer (typically a conversion coating) comprising the reaction product of a polymer P as defined above with a metal of the treated surface or another compound present in said layer.
Specific features and possible embodiments of the invention will now be described in more detail.
Treated metal surface
Any metal surface can be treated with the polymer P of the invention, but the invention is particularly suitable for treating metal surfaces of the following:
-aluminum or an aluminum-based alloy; or (b)
Steel, such as galvanized steel (hot dip galvanized HDG or electrogalvanized EG); or Cold Rolled Steel (CRS); or (b)
-magnesium or magnesium-based alloys; or (b)
Zinc or zinc-based alloys.
Of particular interest to the present invention are the metal surfaces of those of aluminum and aluminum alloys such as aluminum alloy AA5005 or other alloys tested in the appended examples such as series 1xxx, 2xxx, 3xxx, 4xxx, 5xxx, 6xxx such as AA1050, 2024, 3003, 5182, 5754, 6111, 6016, 6060, 6063, 6182.
Conversion coating
When a conversion coating is applied to a metal surface to be treated according to the present invention, it may be obtained by contacting the surface with any conversion composition known in the art.
As an illustrative example, the metal surface may be contacted with the conversion composition by any means known per se, such as dip coating or spray coating in a conversion bath.
The conversion compositions used according to the invention may typically contain fluoroanions and cationic metals, for example compounds such as H 2 CrF 6 Or more preferably chromium-free compounds, such as H 2 TiF 6 、H 2 ZrF 6 、H 2 HfF 6 、H 2 AlF 6 、H 2 SiF 6 、H 2 GeF 6 、H 2 SNF 4 Or HBF 4 。
The conversion composition may also comprise other compounds such as, for example, silane precursors, and/or cerium salts, and/or terbium molybdate.
Furthermore, according to a specific embodiment, the conversion composition may contain all or part of the polymer P used according to the invention for treating surfaces. In this case, the application of the conversion layer itself leads to the surface treatment according to the invention.
In addition, typically, after the conversion layer is formed, the metal surface carrying the conversion layer is treated by contacting it with a polymer P (which typically may be applied to the conversion layer in the form of a solution or suspension of the polymer P, or within a paint, varnish or adhesive composition applied to the conversion layer).
According to a specific embodiment, it is conceivable to use the polymer P both in the conversion composition and in the lacquer, varnish or adhesive applied on the conversion coating.
The following examples illustrate the invention.
Examples
Example 1
Synthesis of Polymer P1 according to the invention
Poly (AA-stat-MAA-stat-allylcatechol) 26/70/4mol%
Polymer P1 was prepared as follows:
at 500mL three-necked round bottomThe flask was charged with 4-allylcatechol (5.50 g,36.6 mmol), 58.4% acrylic acid in water (AA) (1.47 g,11.9 mmol) and 5% 2,2' -azobis (2-methylpropionamidine) dihydrochloride (V-50) (74.49 g,13.7 mmol) in water, having a molar ratio of 4-allylbenzene-1, 2-diol to 3-allylbenzene-1, 2-diol of 60/40. After stirring under nitrogen for 20 minutes, the round bottom flask was placed in an oil bath at 66 ℃. After 10 minutes, two aqueous solutions of 58.4% AA (13.96 g,113.1 mmol) and 58.4% methacrylic acid (MAA) (37.79 g,256.4 mmol) were added dropwise over 2 hours. After completion, two aqueous solutions of 58.4% AA (13.96 g,113.1 mmol) and 58.4% MAA (56.68 g,384.5 mmol) were again added dropwise over 4 hours and 6 hours, respectively. After the last 2 hours of boiling, the round bottom flask was removed from the oil bath and passed through 1 H NMR spectroscopy (AA conversion=99%; MAA conversion=97%; 4-allylcatechol conversion=91%) and by size exclusion chromatography (M w ＝57kg/mol；M n ＝21kg/mol；) The reaction mixture was analyzed.
Proton nuclear magnetic resonance recording using a 300MHz spectrometer from bruck corporation (Brucker) 1 H NMR) spectra. To measure the conversion of AA, MAA and 4-allylcatechol, four drops of the reaction mixture were reacted in about 1g of deuterated water (D 2 O) dilution.
The molar mass was measured by Size Exclusion Chromatography (SEC) equipped with a multi-angle laser light scattering (MALLS) Mini Dawn TREOS detector and a concentration detector (RI detector) of Agilent company (Agilent). The SEC system was run on a three column Agilent Aquagel OH mix H,8 μm, 3x 30cm at a flow rate of 1mL/min and had the following mobile phases: h 2 O 100％vol.、0.1M NaCl、25mM NaH 2 PO 4 、25mM Na 2 HPO 4 Buffer solution (pH 7). The polymer sample has been dissolved in the mobile phase at 0.5wt% for at least 4 hours and then filtered in a microporous filter (0.45 μm). An absolute molar mass is obtained in which the dn/dC of the poly (acrylic acid) is equal to 0.1875mL/g.
Example 2
Use of the Polymer of example 1
Tests have been performed on aluminum alloy panels (AA 5005 from Q-Panel) using common laboratory equipment (beaker, oven, …), powder coating apparatus (GEMA 2C from Industrie Systeses company), and etching chamber (Q-FOG CRH 600L from qfag company).
In each test, the following protocol was applied:
■ Cleaning and etching
It is carried out by immersing each panel to be tested in a combined rinse-etch bath, which is a 1L bath typically made by diluting a commercially available formulation, DBT ALU 200 (available from Chemtec Aertec company) (5 g DBT ALU 200 into 995g water). The panels were immersed in the rinse-etch bath at 50 ℃ with gentle agitation (200 rpm) for 3min. The panel was then rinsed with 1L deionized water.
■ Treatment of
Which is carried out by immersing the panel obtained after the washing/etching of the preceding step in a treatment bath, which is a 1L bath prepared by diluting in water:
zirconium hexafluoride H at a concentration of 200ppm active substance (0.02 wt.%) 2 ZrF 6 The method comprises the steps of carrying out a first treatment on the surface of the And
the additives to be tested (polymer P1 according to example 1 of the invention vs. ACUMER in the comparative example) at concentrations from 50ppm of active substance (0.005 wt%) to 1,000ppm (0.1 wt%) are given in the table below TM 1510)：
The panels were immersed in the treatment bath at 25 ℃ for 2min. It was not rinsed. Excess bath solution was rinsed from the surface with compressed air. The panels were then dried in an oven at 60 ℃ for 30min.
■ And (3) painting:
each panel was then coated with polyester white powder paint (biancobal 9010) from RIPOL company.
Testing
Each panel was then tested according to a protocol similar to those described in the following standards listed below:
acetate spray: t=35 (+/-2) c, [ NaCl ] =50 (+/-5) g/L, ph=3.1-3.3 (ISO 9227)
-scoring protocol: as described in ISO 17872
Degree of rust, as described in ISO 4628-3
Degree of foaming, quoted as described in ISO 4628-2
Results of rusting
Evaluation according to ISO 4628-3
Regardless of the polymer concentration, rust occurred faster with the comparative examples than with the polymers of the present invention.
Foaming results
Evaluation according to ISO 4628-2
Here again, the polymers according to the invention are significantly better than the comparison substances even after 1000 hours.
Claims (18)
1. A polymer P obtained by radical copolymerization of a mixture of:
-acrylic acid;
-methacrylic acid; and
at least one allylcatechol comprising between 30/70 and 70/30 of a mixture of allylcatechol having a molar ratio of 4-allylbenzene-1, 2-diol to 3-allylbenzene-1, 2-diol of the formula
。
2. The polymer P as claimed in claim 1, having a molecular weight of between 10 and 150 kDa.
3. The polymer P as claimed in claim 1, which contains Acrylic Acid (AA) in an amount of from 10 to 90% by mol; methacrylic acid (MAA) in an amount of 1 to 70% by mol, and allylcatechol in an amount of 1 to 20% by mol, each molar ratio being calculated based on the total amount of AA, MAA and allylcatechol.
4. Use of at least one polymer P as claimed in any of claims 1 to 3 for treating metal surfaces intended to be coated with lacquers, varnishes or adhesives.
5. The use of claim 4, wherein the metal surface is a surface comprising a metal selected from the group consisting of aluminum, steel, zinc, magnesium, and alloys thereof.
6. The use of claim 5, wherein the metal surface is a surface of aluminum or an aluminum alloy.
7. The use of any one of claims 4 to 6, wherein a conversion composition is applied on the metal surface to form a conversion coating thereon, and wherein:
-the conversion composition comprises all or part of the polymer P as additive; and/or
-applying the conversion coating on the metal surface and applying all or part of the polymer P on the conversion coating.
8. The use as claimed in any of claims 4 to 6, wherein all or part of the polymer P is present in a lacquer, varnish or coating which is applied on the surface.
9. The use of claim 8, wherein the paint, varnish or coating is applied to the metal surface after the conversion coating has been applied to the surface.
10. A process for coating a metal surface with paint, varnish or adhesive, which comprises the step of treating said surface with at least one composition comprising at least one polymer P as defined in any one of claims 1 to 3.
11. The method of claim 10 for coating a metal surface with paint.
12. The method of claim 10 or 11, wherein the composition comprising the polymer P is:
-a conversion composition comprising a polymer P; and/or
-a solution or dispersion of the polymer P; and/or
The paint, varnish or adhesive comprising the polymer P.
13. The method of claim 12, wherein the solution or dispersion of the polymer P is applied to the surface to be treated after the conversion coating is applied to the surface.
14. A conversion composition comprising at least one polymer P as defined in any of claims 1 to 3.
15. A paint, varnish or adhesive composition containing at least one polymer P as defined in any of claims 1 to 3.
16. A material comprising a metal surface treated wholly or partly (i) with at least one polymer P as defined in any one of claims 1 to 3 and (ii) covered with paint, varnish or adhesive, said material being a material having a metal surface wholly or partly covered by:
-at least one coating comprising at least one polymer P as defined in any one of claims 1 to 3;
and/or
-a layer comprising the reaction product of the at least one polymer P as defined in any one of claims 1 to 3 with the metal of the treated surface or another compound present in the layer.
17. The material of claim 16, wherein the at least one coating is a conversion coating and/or a paint, varnish or adhesive layer.
18. The material of claim 16, wherein the layer is a conversion coating.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP18208625.6 | 2018-11-27 | ||
| EP18208625.6A EP3659716A1 (en) | 2018-11-27 | 2018-11-27 | Polymers for metal surface treatment |
| PCT/EP2019/082792 WO2020109413A1 (en) | 2018-11-27 | 2019-11-27 | Polymers for metal surface treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113015582A CN113015582A (en) | 2021-06-22 |
| CN113015582B true CN113015582B (en) | 2023-12-05 |
Family
ID=64500282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980074620.0A Active CN113015582B (en) | 2018-11-27 | 2019-11-27 | Polymer for metal surface treatment |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20220002456A1 (en) |
| EP (2) | EP3659716A1 (en) |
| CN (1) | CN113015582B (en) |
| BR (1) | BR112021006893A2 (en) |
| WO (1) | WO2020109413A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021233715A1 (en) * | 2020-05-19 | 2021-11-25 | Rhodia Operations | Polymers for metal surface treatment |
| WO2022073879A1 (en) | 2020-10-09 | 2022-04-14 | Rhodia Operations | Metal surface treatment |
| EP4225856A1 (en) | 2020-10-09 | 2023-08-16 | Rhodia Operations | Metal surface treatment |
| EP4006116A1 (en) | 2020-11-26 | 2022-06-01 | Rhodia Operations | Metal surface treatment |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4761189A (en) * | 1982-12-23 | 1988-08-02 | Gerhard Collardin Gmbh | Process and aqueous compositions for treating metal surfaces |
| US5534082A (en) * | 1992-04-01 | 1996-07-09 | Henkel Corporation | Composition and process for treating metal |
| CN106574372A (en) * | 2014-01-23 | 2017-04-19 | 凯密特尔有限责任公司 | Method for coating metal surfaces, substrates coated in this way, and use thereof |
| WO2018119376A1 (en) * | 2016-12-22 | 2018-06-28 | Henkel Ag & Co. Kgaa | Treatment of conversion-coated metal substrates with preformed reaction products of catechol compounds and functionalized co-reactant compounds |
| WO2018119368A1 (en) * | 2016-12-22 | 2018-06-28 | Henkel Ag & Co. Kgaa | Reaction products of catechol compounds and functionalized co-reactant compounds for metal pretreatment applications |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4191596A (en) | 1978-09-06 | 1980-03-04 | Union Carbide Corporation | Method and compositions for coating aluminum |
| US4921552A (en) | 1988-05-03 | 1990-05-01 | Betz Laboratories, Inc. | Composition and method for non-chromate coating of aluminum |
| US5641542A (en) | 1995-10-11 | 1997-06-24 | Betzdearborn Inc. | Chromium-free aluminum treatment |
| KR101942325B1 (en) * | 2012-02-10 | 2019-04-11 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Anticorrosion coatings |
-
2018
- 2018-11-27 EP EP18208625.6A patent/EP3659716A1/en not_active Ceased
-
2019
- 2019-11-27 BR BR112021006893-7A patent/BR112021006893A2/en not_active Application Discontinuation
- 2019-11-27 WO PCT/EP2019/082792 patent/WO2020109413A1/en unknown
- 2019-11-27 EP EP19809837.8A patent/EP3887068B1/en active Active
- 2019-11-27 CN CN201980074620.0A patent/CN113015582B/en active Active
- 2019-11-27 US US17/293,543 patent/US20220002456A1/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4761189A (en) * | 1982-12-23 | 1988-08-02 | Gerhard Collardin Gmbh | Process and aqueous compositions for treating metal surfaces |
| US5534082A (en) * | 1992-04-01 | 1996-07-09 | Henkel Corporation | Composition and process for treating metal |
| CN106574372A (en) * | 2014-01-23 | 2017-04-19 | 凯密特尔有限责任公司 | Method for coating metal surfaces, substrates coated in this way, and use thereof |
| WO2018119376A1 (en) * | 2016-12-22 | 2018-06-28 | Henkel Ag & Co. Kgaa | Treatment of conversion-coated metal substrates with preformed reaction products of catechol compounds and functionalized co-reactant compounds |
| WO2018119368A1 (en) * | 2016-12-22 | 2018-06-28 | Henkel Ag & Co. Kgaa | Reaction products of catechol compounds and functionalized co-reactant compounds for metal pretreatment applications |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3659716A1 (en) | 2020-06-03 |
| US20220002456A1 (en) | 2022-01-06 |
| CN113015582A (en) | 2021-06-22 |
| EP3887068A1 (en) | 2021-10-06 |
| BR112021006893A2 (en) | 2021-07-20 |
| WO2020109413A1 (en) | 2020-06-04 |
| EP3887068B1 (en) | 2022-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113015582B (en) | Polymer for metal surface treatment | |
| JP3280080B2 (en) | Metal surface treatment method with chromium-free coating type acidic composition | |
| CN113165013A (en) | Surface treatment of metals | |
| EP2094880A1 (en) | Process for treating metal surfaces | |
| CN107208272B (en) | Method for the adhesive coating of metal surfaces, in particular aluminum materials | |
| JP6837332B2 (en) | Chemical conversion agent, manufacturing method of chemical conversion film, metal material with chemical conversion film, and coated metal material | |
| KR20160091906A (en) | Method for treating surface of zinc-aluminum-magnesium alloy-plated steel sheet | |
| RU2363769C2 (en) | Coating composition | |
| JP7052137B1 (en) | Chemical treatment agents, surface treatment metals, and surface treatment methods | |
| JP2018104689A (en) | Coating composition excellent in corrosion resistance and lubricity and coating steel sheet using the same | |
| US20210253870A1 (en) | Method for treating surfaces of aluminum containing substrates | |
| CA2663659A1 (en) | Non-chrome thin organic-inorganic hybrid coating on zinciferous metals | |
| JP7117292B2 (en) | Improved method for corrosion protective pretreatment of metal surfaces including steel, galvanized steel, aluminum, aluminum alloys, magnesium and/or zinc-magnesium alloys | |
| JP2023547737A (en) | Treatment of metal surfaces with copolymers containing acidic aqueous compositions | |
| EP4237597A1 (en) | Zr, mo and acid-functional polymer containing aqueous compositions for treatment of metallic surfaces | |
| CN115667439A (en) | Polymer for metal surface treatment | |
| US20230340306A1 (en) | Metal surface treatment | |
| CN116783326A (en) | Improved Cr (III) -based in-situ drying coating composition for galvanized steel | |
| JP2023547738A (en) | Treatment of metal surfaces with OH-functional copolymers containing acidic aqueous compositions | |
| CN116568411A (en) | Metal surface treatment | |
| CN109715853A (en) | The adhesion promotor that can be used as the reaction product acquisition of diamines or polyamines and alpha, beta-unsaturated carboxylic acid derivative is used for the purposes of Treatment of Metal Surface |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |